A metal compound containing a dihydronaphthalene structure, and a preparation method and application thereof

Abstract

The present application relates to a kind of metal compound containing dihydronaphthalene structure and its preparation method and application, the metal compound containing dihydronaphthalene structure has the structure shown in formula (I).The metal compound containing dihydronaphthalene structure provided by the present application takes dihydronaphthalene as skeleton, i.e. rigid with aromatic ring, also has the flexibility of cycloalkyl, is complexed with the fourth vice (IVB group) group metal to form stable complex.The metal compound has the characteristics such as simple preparation, high activity, good copolymerization performance, the catalyst composition of its composition is suitable for olefin slurry polymerization to prepare polyolefin material, and the obtained polymer has the characteristics such as good form, low cost, high molecular weight, low extraction rate and higher bulk density.

Description

Technical Field

[0001] The present invention relates to the technical field of olefin polymer catalysts, in particular to a metal compound containing a dihydronaphthalene structure, a preparation method and application thereof. Background Art

[0002] Polyolefin materials have become a leader among polymer materials due to their diverse variety, high production volume, and wide range of applications. Polyolefin elastomers, with their excellent compatibility, superior processability, and weather resistance, have become a star among polyolefin materials, gaining widespread popularity and application in defense science, agriculture, automotive, and other fields. Polyolefin catalysts are central to the development of polyolefin materials. Recently reported catalysts for ethylene homopolymerization and copolymerization, particularly those with excellent thermal stability, are crucial for the preparation of polyolefin elastomers (POE).

[0003] Currently, the industry uses a homogeneous high-temperature solution process to produce polyolefin elastomers. This process is energy-intensive, produces polymers with poor morphology and low bulk density, and typically uses methylaluminoxane (MAO) as a catalyst, increasing costs. The constrained geometry catalyst (EP0416815A2), developed by Dow Chemical in the 1990s and having the structure of Formula I, produces polyolefin elastomers with low molecular weight and poor catalytic performance at low temperatures.

[0004]

[0005] Stephen et al. (Stephen, A. Miller, et al. Isotactic-Hemiisotactic Polypropylene from C1-Symmetric ansa-Metallocene Catalysts: A New Strategy for the Synthesis of Elastomeric Polypropylene[J]. Organometallics, 2002.) disclose a catalyst having a structure of Formula 2, which is used to catalyze olefin polymerization. However, the catalyst has the disadvantages of low polymer molecular weight, poor polymer morphology, easy blockage of the reactor during industrial production, and increased cost caused by the use of a large amount of MAO during the polymerization process.

[0006]

[0007] Froese et al. (Froese RDJ, Jazdzewski BA, Klosin J, et al. Imino-Amido Hfand Zr Complexes: Synthesis, Isomerization, and Olefin Polymerization [J]. Organometallics, 2011, 30 (2): 251–262.) reported a catalyst having the structure of Formula 3 for catalytic olefin polymerization. However, the catalyst had disadvantages such as low catalytic activity, low comonomer insertion rate, and wide molecular weight distribution, which led to a decrease in the mechanical properties of the material and limited its application.

[0008]

[0009] Therefore, it is of great significance to provide a catalyst with the advantages of high catalytic activity, high comonomer insertion rate, and narrow molecular weight distribution. Summary of the Invention

[0010] To address the above-mentioned technical problems, the present invention provides a metal compound containing a dihydronaphthalene structure, as well as its preparation method and application. The metal compound containing a dihydronaphthalene structure provided by the present invention comprises a dihydronaphthalene skeleton and is complexed with a Group IV (IVB) metal, as specifically shown in the structure of Formula (I). This dihydronaphthalene metal compound utilizes a hydrogenated naphthalene skeleton, which combines the rigidity of an aromatic ring with the flexibility of a cycloalkyl group. The flexibility of the cycloalkyl group facilitates the insertion of comonomers. Furthermore, the nitrogen in this metal compound is covalently bonded, making the resulting metal compound more stable, achieving the goal of catalyzing olefin polymerization at room temperature and exhibiting excellent catalytic performance. By modifying the benzene ring connected to the central nitrogen atom to alter the position, steric hindrance, and power supply capacity of the substituents, the metal center is further modified. Heteroatoms are introduced into the benzene ring, creating a unique "barrier effect." By adjusting the steric hindrance and electronic effects of the side arms, the insertion of comonomers is influenced, thereby enabling precise control of the polymer structure and producing polymers with high molecular weight and high comonomer insertion rates. It can catalyze the homopolymerization of ethylene to produce ultra-high molecular weight polyethylene; it can catalyze the copolymerization of ethylene with α-olefins such as 1-hexene and 1-octene to produce copolymers with high molecular weight, high comonomer insertion rate and narrow molecular weight distribution. The polymers have high bulk density and low extraction rate.

[0011] To achieve this object, the present invention adopts the following technical solutions:

[0012] In a first aspect, the present invention provides a metal compound containing a dihydronaphthalene structure, wherein the metal compound containing a dihydronaphthalene structure has a structure shown in formula (I):

[0013]

[0014] wherein R1is selected from hydrogen, halogen, substituted or unsubstituted C1-C 20 alkyl, substituted or unsubstituted C3-C 20 cycloalkyl, substituted or unsubstituted C6-C 18 aryl, substituted or unsubstituted C4-C 18 heteroaryl; R2is selected from hydrogen, halogen, substituted or unsubstituted C1-C 20 alkyl, substituted or unsubstituted C1-C 20 alkyl, substituted or unsubstituted C1-C 16 alkoxy;

[0015] X is selected from halogen, substituted or unsubstituted C1-C 20 alkyl, -NR4R5; said R4and R5are the same or different, each independently selected from C1-C8alkyl;

[0016] M is selected from Group IVB metals;

[0017] when the group contains a heteroatom, the heteroatom is selected from one or a combination of two or more of O, S, N, P, Si;

[0018] said substituted group is selected from halogen, C1-C8alkyl, C1-C8alkoxy, C6-C 10 aryl, C6-C 10 heteroaryl.

[0019] wherein C1-C 20 may be C1, C2, C4, C6, C8, C 10 , C 12 , C 15 , C 18 or C 20 ; C3-C 20 may be C3, C4, C5, C8, C 10 , C 12 , C 15 , C 18 or C 20 ; C6-C 18 may be C6, C 10 , C 12 , C 14 or C 18 ; C4-C 18 may be C4, C5, C8, C9, C 12 , C 13 , C 14 , C 15 , C 16 or C18 etc.; C1-C 16 Can be C1, C2, C4, C6, C8, C 10 、C 12 、C 14 or C 16 etc.; C1-C8 can be C1, C2, C3, C4, C5, C6, C7 or C8; C6-C 10 Can be C6, C7, C8, C9 or C 10 .

[0020] Preferably, R1 is selected from hydrogen, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 14 Aryl, substituted or unsubstituted C4-C 12 Heteroaryl.

[0021] Among them, C1-C4 can be C1, C2, C3 or C4; C3-C6 can be C3, C4, C5 or C6; C6-C 14 Can be C6, C9, C 10 、C 12 or C 14 ;C4-C 12 It can be C4, C5, C6, C7, C8, C9, C 10 、C 11 or C 12 .

[0022] Preferably, R1 is selected from hydrogen, chlorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-tert-butylphenyl, 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl.

[0023] Preferably, R2 is selected from hydrogen, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C8 alkoxy.

[0024] Preferably, R2 is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or methoxy.

[0025] Preferably, X is selected from halogen, substituted or unsubstituted C1-C4 alkyl, -NR4R5, wherein R4 and R5 are the same or different and are independently selected from C 1-8 alkyl.

[0026] Preferably, X is selected from chlorine, methyl, benzyl or dimethylamino.

[0027] Preferably, M is selected from titanium, zirconium or hafnium.

[0028] Preferably, the metal compound containing a dihydronaphthalene structure is selected from any one of the following compounds:

[0029]

[0030] In a second aspect, the present invention provides a method for preparing the metal compound containing a dihydronaphthalene structure according to the first aspect, the preparation method comprising the following steps:

[0031] (1) 1,4-dihydro-naphthalene-2,3-dione reacts with morpholine to obtain the intermediate 2-(4-morpholino)-1,4-dihydro-naphthalene-3-one;

[0032]

[0033] (2) mixing the intermediate 2-(4-morpholino)-1,4-dihydro-naphthalen-3-one described in step (1) with the compound represented by formula II, adding a catalyst, and reacting to obtain intermediate 2;

[0034]

[0035] (3) mixing the intermediate 2 described in step (2) with the compound represented by formula III, adding a desiccant and a catalyst, and reacting to obtain intermediate 3;

[0036]

[0037] (4) mixing the compound represented by Formula IV and the compound represented by Formula V, adding the intermediate 3 described in step (3) to carry out reaction a to obtain the metal compound containing a dihydronaphthalene structure;

[0038]

[0039] Alternatively, the compound represented by formula IV is directly added to the intermediate 3 described in step (3) to carry out reaction b to obtain the metal compound containing a dihydronaphthalene structure;

[0040]

[0041] Alternatively, the compound represented by formula VI is directly added to the intermediate 3 described in step (3) to carry out reaction c to obtain the metal compound containing a dihydronaphthalene structure;

[0042]

[0043] Preferably, the reaction in steps (1) to (4) is carried out in an anhydrous solvent, and the anhydrous solvent includes any one of benzene, toluene, xylene or n-hexane, or a combination of at least two thereof.

[0044] Preferably, the molar ratio of 1,4-dihydro-naphthalene-2,3-dione to morpholine in step (1) is 1:(0.9-1), for example, it can be 1:0.9, 1:0.91, 1:0.92, 1:0.93, 1:0.94, 1:0.95, 1:0.96, 1:0.97, 1:0.98, 1:0.99 or 1:1, etc.

[0045] Preferably, the reaction in step (1) is carried out under reflux.

[0046] Preferably, the reaction time of step (1) is 5 to 10 h, for example, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h or 10 h.

[0047] Preferably, after the reaction in step (1) is completed, the anhydrous solvent is removed by vortexing under reduced pressure.

[0048] Preferably, the molar ratio of the 2-(4-morpholine)-1,4-dihydro-naphthalen-3-one in step (2) to the compound represented by formula II is 1:(0.6-1.0), for example, it can be 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95 or 1:1.0, etc.

[0049] Preferably, the compound represented by formula II in step (2) is added in batches, more preferably in three batches.

[0050] Preferably, the mixing in step (2) is carried out under stirring.

[0051] Preferably, the molar ratio of the 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one to the catalyst in step (2) is 1:(0.0058-0.029), for example, it can be 1:0.0058, 1:0.008, 1:0.01, 1:0.015, 1:0.02, 1:0.025 or 1:0.029, etc.

[0052] Preferably, the catalyst in step (2) comprises p-toluenesulfonic acid.

[0053] Preferably, the reaction in step (2) is carried out under reflux.

[0054] Preferably, the reaction time of step (2) is 10 to 18 hours, for example, it can be 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours or 18 hours.

[0055] Preferably, after the reaction in step (2) is completed, the reaction solution is cooled to room temperature, filtered, the anhydrous solvent is removed under reduced pressure, and column chromatography is performed to obtain intermediate 2.

[0056] Preferably, the eluents in the column chromatography are petroleum ether and ethyl acetate in a volume ratio of (1-20):1, for example, 1:1, 2:1, 5:1, 8:1, 10:1, 12:1, 15:1, 18:1 or 20:1.

[0057] In the present invention, column chromatography can be performed using a gradient elution with a volume ratio of (1 to 20):1 of petroleum ether and ethyl acetate as the eluent, or a fixed ratio of (1 to 20):1. If gradient elution is used, the elution ratios are illustratively 1:1, 5:1, 10:1, 15:1, and 20:1, respectively.

[0058] Preferably, the molar ratio of the intermediate 2 in step (3) to the compound represented by formula III is 1:(1-5), for example, it can be 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, etc.

[0059] Preferably, the mixing in step (3) is carried out under stirring.

[0060] Preferably, the desiccant in step (3) comprises molecular sieve.

[0061] Preferably, the catalyst in step (3) comprises formic acid.

[0062] Preferably, the molar ratio of the intermediate 2 to the catalyst in step (3) is 1:(0.1-0.5), for example, it can be 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45 or 1:0.5, etc.

[0063] Preferably, the reaction in step (3) is carried out under reflux.

[0064] Preferably, the reaction time of step (3) is 10 to 18 hours, for example, it can be 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours or 18 hours.

[0065] Preferably, after the reaction in step (3) is completed, the reaction solution is filtered to remove the desiccant, the anhydrous solvent is removed under reduced pressure, and column chromatography is performed to obtain intermediate 3.

[0066] Preferably, the column used for column chromatography is treated with triethylamine.

[0067] Preferably, the eluent used for the column chromatography includes petroleum ether and ethyl acetate in a volume ratio of (1:50) to (100:1).

[0068] In the present invention, specific eluents of petroleum ether and ethyl acetate are used in the column chromatography process, and the elution can be a fixed ratio or a gradient elution, such as eluting in a gradient of 1:50, 1:10, 1:1, 10:1, 20:1, 50:1, 80:1, and 100:1, but the elution is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0069] Preferably, the eluent further comprises triethylamine.

[0070] Preferably, the added volume of the triethylamine is 1-5% of the sum of the added volumes of the petroleum ether and ethyl acetate, for example, it can be 1%, 2%, 3%, 4% or 5%.

[0071] Preferably, the compound represented by formula IV in step (4) is dissolved in an anhydrous solvent before being mixed and stirred with the compound represented by formula V.

[0072] Preferably, when the amount of the compound represented by formula IV added in step (4) is 1 mmol, the volume of the anhydrous solvent added is 15 to 50 mL, for example, 18 mL, 20 mL, 22 mL, 25 mL, 28 mL, 30 mL, 35 mL, 40 mL or 45 mL.

[0073] Preferably, the molar ratio of formula IV, formula V and intermediate 3 in the reaction a of step (4) is 1:(4-6):1, for example, it can be 1:4:1, 1:4.2:1, 1:4.5:1, 1:4.8:1, 1:5:1, 1:5.2:1, 1:5.5:1, 1:5.8:1 or 1:6:1, etc.

[0074] Preferably, the mixing and stirring in step (4) is carried out at low temperature.

[0075] Preferably, the low temperature is -45°C to 10°C, for example, -45°C, -40°C, -35°C, -30°C, -25°C, -20°C, -15°C, -10°C, -5°C, 0°C or 5°C.

[0076] Preferably, the stirring time in step (4) is 1.5 to 2.5 h, for example, it can be 1.6 h, 1.7 h, 1.8 h, 1.9 h, 2 h, 2.1 h, 2.2 h, 2.3 h, 2.4 h or 2.5 h.

[0077] Preferably, the reaction a in step (4) is first stirred at -45°C to 10°C for 1.5 to 2.5 hours, then heated to room temperature and stirred for 4 to 6 hours (for example, 4.2 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours or 5.8 hours, etc.).

[0078] Preferably, the molar ratio of formula IV to intermediate 3 in reaction b of step (4) is 1:(1-2), for example, it can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8 or 1:1.9, etc.

[0079] Preferably, the reaction b in step (4) is first stirred at -45°C to 10°C (for example, -45°C, -40°C, -35°C, -30°C, -25°C, -20°C, -15°C, -10°C, -5°C, 0°C or 5°C, etc.) for 1.5 to 2.5h (for example, 1.5h, 1.8h, 1.9h, 2.0h, 2.2h, 2.4h or 2.5h, etc.), and then heated to room temperature and stirred for 4 to 6h (for example, 4.2h, 4.5h, 4.8h, 5h, 5.2h, 5.5h or 5.8h, etc.).

[0080] Preferably, the molar ratio of formula VI to intermediate 3 in reaction c of step (4) is 1:(1-2), for example, it can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8 or 1:1.9, etc.

[0081] Preferably, the reaction c in step (4) is stirred at 50°C to 100°C (for example, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C, etc.) for 4 to 10 h (for example, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h or 9.5 h, etc.).

[0082] Preferably, in the synthesis method in which the compound represented by Formula IV or the compound represented by Formula VI directly reacts with the intermediate 3 described in step (3), the compound represented by Formula IV or the compound represented by Formula VI is first dissolved in an anhydrous solvent, and when the amount of the compound represented by Formula IV or the compound represented by Formula VI added is 1 mmol, the volume of the anhydrous solvent added is 15 to 50 mL.

[0083] Preferably, after the reaction a, b or c in step (4) is completed, the anhydrous solvent is removed under reduced pressure, and extraction is performed with a good solvent to obtain the metal compound containing a dihydronaphthalene structure.

[0084] Preferably, the reactions in steps (1), (3) and (4) are all carried out under a protective gas atmosphere, wherein the protective gas comprises any one of nitrogen, argon and helium or a combination of at least two of them.

[0085] Preferably, the good solvent in step (4) includes any one of n-hexane, n-pentane, n-heptane, cyclohexane, methylcyclohexane or toluene, or a combination of at least two thereof.

[0086] In a third aspect, the present invention provides a catalyst composition for polymerizing olefins, wherein the catalyst composition comprises the metal compound containing a dihydronaphthalene structure as described in the first aspect, a co-catalyst and an activator.

[0087] Preferably, the molar ratio of the co-catalyst to the metal compound containing a dihydronaphthalene structure according to claim 1 is (0.001-100000):1, for example, it can be 0.001:1, 0.01:1, 0.1:1, 0.2:1, 1:1, 10:1, 100:1, 500:1, 1000:1, 10000:1 or 100000:1, etc., preferably (0.2-500):1.

[0088] Preferably, the co-catalyst comprises an organometallic compound and / or an organoboron compound.

[0089] Preferably, the organometallic compound and / or organoboron compound comprises M 3 (X 10 ) n1 (X 11 ) 3-n1 、M 4 (X 10 ) n2 (X 11 ) 2-n2 or M 5 X 10 Any of the following;

[0090] Among them, M 3 is boron or aluminum, n1 is 1-3 (for example, 1, 2 or 3); M 4 is magnesium or zinc, n2 is 1-2 (for example, 1 or 2, etc.); M 5 For Li;

[0091] X 10 Selected from hydrogen, C1-C 20 Hydrocarbon; X 11 Selected from hydrogen, halogen, C1-C 20 Hydrocarbon or C1-C 20 alkoxy;

[0092] Preferably, the M 3 (X 10 ) n1 (X 11 ) 3-n1 The present invention includes any one or a combination of at least two of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide or diethylaluminum chloride.

[0093] Preferably, the M4 (X 10 ) n2 (X 11 ) 2-n2 The present invention comprises any one of dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc or dineopentylzinc, or a combination of at least two thereof.

[0094] Preferably, the activator comprises any one or a combination of at least two of an organic boron compound, an organic borate compound, an ionizing ionic compound, an aluminoxane compound or a solid oxide (activator-support).

[0095] Preferably, the solid oxide comprises any one of silica, alumina, titania, zirconia, magnesia, boria, calcium oxide, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, silica-boria, alumina-titania, titania-zirconia, alumina-zirconia, alumina-boria, zinc aluminate, aluminum phosphate, aluminum phosphate, aluminum phosphate-silica, magnesium aluminate, boehmite or heteropolytungstate, or a combination of at least two thereof.

[0096] Preferably, the solid oxide needs to be calcined.

[0097] Preferably, the calcination is carried out under a protective gas atmosphere, and the protective gas includes any one of nitrogen, argon and helium, or a combination of at least two of them.

[0098] Preferably, the calcination includes low-temperature calcination and high-temperature calcination.

[0099] Preferably, the temperature of the low-temperature calcination is 200-500°C, for example, 220°C, 240°C, 260°C, 280°C, 300°C, 350°C, 400°C, 450°C or 500°C, preferably 200-300°C.

[0100] Preferably, the low-temperature calcination time is 1 to 10 h, for example, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h, etc., preferably 2 to 5 h.

[0101] Preferably, the high temperature calcination temperature is 600-900°C, for example, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C or 900°C.

[0102] Preferably, the high-temperature calcination time is 4 to 40 h, for example, 4 h, 6 h, 8 h, 10 h, 15 h, 20 h, 25 h, 30 h, 35 h or 40 h, etc., preferably 4 to 10 h.

[0103] In a fourth aspect, the present invention provides a use of the metal compound containing a dihydronaphthalene structure described in the first aspect or the catalyst composition described in the third aspect in an olefin polymerization reaction.

[0104] The catalyst composition provided in the present invention can contact with olefin monomers under polymerization conditions to catalyze the monomers to quickly form olefin polymers.

[0105] The metal compound containing dihydronaphthalene structure provided by the present invention is pre-contacted with at least one organoaluminum compound and olefin monomer to form a pre-contact mixture, and then the pre-contact mixture is contacted with a solid oxide activator-support to form an active catalyst. When preparing catalyst composition in this way, usually (but not necessarily) a part of the organoaluminum compound can be added to the pre-contact mixture, and another part of the organoaluminum compound can be added to the post-contact mixture prepared when the pre-contact mixture can be contacted with the solid oxide activator. All organoaluminum compounds are used to prepare catalysts in the pre-contact or post-contact steps. Alternatively, all catalyst components can be contacted in a single step.

[0106] Preferably, the olefin monomer includes any one of ethylene, propylene, butene, pentene, hexene, heptene, octene, styrene or 4-methyl-1-pentene, or a combination of at least two thereof.

[0107] Compared with the prior art, the present invention has at least the following beneficial effects:

[0108] (1) The metal compound containing a dihydronaphthalene structure provided by the present invention adopts a hydrogenated naphthalene skeleton, that is, it has the rigidity of an aromatic ring and the flexibility of a cycloalkyl group; the flexibility of the cycloalkyl group provides the possibility for the insertion of a comonomer; and the nitrogen in the metal compound exists in the form of a covalent bond, making the formed metal compound more stable, and can be used to catalyze olefin polymerization reactions at room temperature and exhibit good catalytic performance;

[0109] (2) The metal compound containing a dihydronaphthalene structure provided by the present invention modifies the benzene ring connected to the middle nitrogen atom to change the position of the substituent, the size of the steric hindrance and the strength of the power supply capacity, thereby playing a better modification role on the metal center; introduces heteroatoms on the benzene ring to form a unique "barrier effect"; by adjusting the size of the steric hindrance and the electronic effect of the side arm, it affects the insertion of the comonomer in the olefin copolymerization reaction, thereby achieving precise control of the polymer structure and preparing a polymer with high molecular weight and high comonomer insertion rate. DETAILED DESCRIPTION

[0110] For the convenience of understanding the present invention, the present invention is given below with examples. It should be understood by those skilled in the art that the examples are only for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0111] The materials and reagents used in the following examples are all commercially available. The details are as follows:

[0112] 1,4-Dihydro-2,3-naphthalenedione: AR, Innochem

[0113] Morpholine: AR, Innochem

[0114] 2-Amino-4,6-dimethylphenol: AR, Aladdin

[0115] 2-Amino-4,6-di-tert-butylphenol: AR, Aladdin

[0116] 2-Amino-4,6-diisobutylphenol: AR, Aladdin

[0117] 2-Amino-4,6-dicyclohexylphenol: AR, Aladdin

[0118] 2-Amino-4,6-difluorophenol: AR, Aladdin

[0119] 2-Aminophenol: AR, Aladdin

[0120] Aniline: AR, Innochem

[0121] n-Octylamine: AR, Innochem

[0122] Tert-butylamine: AR, Innochem

[0123] n-Hexylamine: AR, Innochem

[0124] n-Butylamine: AR, Innochem

[0125] n-Propylamine: AR, Innochem

[0126] Cyclohexylamine: AR, Innochem

[0127] Cyclooctylamine: AR, Innochem

[0128] 2,6-Diisopropylaniline: AR, Aladdin

[0129] 4-Methoxyaniline: AR, Innochem

[0130] Methylmagnesium bromide ether solution: 3M, AR, Aladdin

[0131] p-Toluenesulfonic acid: AR, Aladdin

[0132] Toluene: AR, Aladdin

[0133] n-Hexane: AR, Aladdin

[0134] Petroleum ether: 60-90℃, Sinopharm

[0135] Ethyl acetate: AR, Aladdin

[0136] Deuterated chloroform: AR, Acros

[0137] Industrial ethanol: 95%, Beijing Chemical Reagent Company

[0138] Triphenylcarbonium tetrakis(pentafluorophenyl)borate: AR, Aladdin

[0139] MAO (methylaluminoxane): AR, Aladdin

[0140] 1-Octene: AR, Acros

[0141] Silica gel: AR, 200-300 mesh, Shanghai Wusi Chemical Reagent Company

[0142] Titanium tetrachloride: AR, Aladdin

[0143] Zirconium tetrachloride: AR, Aladdin

[0144] Hafnium tetrachloride: AR, Aladdin

[0145] Tetrabenzylhafnium: AR, Aladdin

[0146] Other reagents or raw materials not otherwise specified were commercially available.

[0147] In the present invention, the compounds in the preparation examples, examples and comparative examples were all tested and characterized using a nuclear magnetic resonance spectrometer (Brucker ARX-400).

[0148] Preparation Example 1

[0149] This preparation example provides a preparation method for the compound 2-(4-morpholino)-1,4-dihydro-naphthalen-3-one, which comprises the following steps:

[0150] Under a nitrogen atmosphere, 1,4-dihydro-2,3-naphthalenedione (16.0 g, 100 mmol) was mixed with morpholine (7.84 g, 90 mmol) and refluxed in 150 mL of toluene for 8 h. The toluene was removed under reduced pressure to give compound 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one (18.98 g, yield 92%).

[0151] The NMR characterization data of the compound 2-(4-morpholino)-1,4-dihydro-naphthalen-3-one are as follows:

[0152] 1 H NMR (400MHz, C6D6): δ7.35-7.20 (m, 4H), 6.38 (s, 1H), 4.20 (s, 2H), 3.65 (t, 4H, J = 7.1Hz), 3.47 (t, 4H, J = 7.3Hz).

[0153] Preparation Example 2

[0154] This preparation example provides a preparation method for the compound 3-((2-hydroxy-3,5-di-tert-butylphenyl)-amino)naphthalene-2-one, which comprises the following steps:

[0155] The compound 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one (2.29 g, 10 mmol) shown in Preparation Example 1 was mixed with 2-hydroxy-3,5-di-tert-butylaniline (1.99 g, 9 mmol) in three times, 50 mg of p-toluenesulfonic acid was added as a catalyst, and the mixture was refluxed in 50 mL of dry toluene solvent for 18 hours; cooled to room temperature, the reaction system was filtered, and the toluene was removed under reduced pressure. The mixture was purified by column chromatography with petroleum ether and ethyl acetate as the eluent in a volume ratio of 10:1 to obtain the compound 3-((2-hydroxy-3,5-di-tert-butylphenyl)-amino)naphthalene-2-one (2.40 g, yield 73.4%).

[0156] The NMR characterization data of the compound 3-((2-hydroxy-3,5-di-tert-butylphenyl)-amino)naphthalene-2-one are as follows:

[0157] 1 H NMR (400MHz, C6D6): δ7.34-7.32(m,1H),7.26(dd,1H),7.21(dd,2H,J=9.1,5.2Hz),7.11(s,1H),6.75 (dd,1H,J=8.3Hz),5.98(dd,1H,J=8.5,4.4Hz),5.35(s,1H),4.20(s,2H),4.00(s,1H),1.35(s,18H).

[0158] Preparation Example 3

[0159] This preparation example provides a preparation method for the compound 3-((2-hydroxy-3,5-dimethylphenyl)-amino)naphthalene-2-one, which comprises the following steps:

[0160] The compound 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one (2.29 g, 10 mmol) shown in Preparation Example 1 was mixed with 2-hydroxy-3,5-dimethylaniline (1.23 g, 9 mmol) in three times, 50 mg of p-toluenesulfonic acid was added as a catalyst, and the mixture was refluxed in 50 mL of dry toluene solvent for 18 hours; cooled to room temperature, the reaction system was filtered, and the toluene was removed under reduced pressure. The mixture was purified by column chromatography with petroleum ether and ethyl acetate as the eluent in a volume ratio of 10:1 to obtain the compound 3-((2-hydroxy-3,5-dimethylphenyl)-amino)naphthalene-2-one (2.16 g, yield 85.8%).

[0161] The NMR characterization data of the compound 3-((2-hydroxy-3,5-dimethylphenyl)-amino)naphthalene-2-one are as follows:

[0162] 1 H NMR (400MHz, C6D6): δ7.34-7.32(m,1H),7.26(dd,1H),7.21(dd,2H,J=9.1,5.2Hz),7.11(s,1H),6.96(d,1H ,J=8.3Hz,),6.29(dd,1H,J=8.6,4.2Hz),5.33(s,1H),4.20(s,2H),4.00(s,1H),2.34(s,3H),2.15(s,3H).

[0163] Preparation Example 4

[0164] This preparation example provides a preparation method for the compound 3-((2-hydroxyphenyl)-amino)naphthalene-2-one, which comprises the following steps:

[0165] The compound 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one (2.29 g, 10 mmol) shown in Preparation Example 1 was mixed with 2-hydroxyaniline (0.98 g, 9 mmol) in three times, 50 mg of p-toluenesulfonic acid was added as a catalyst, and the mixture was refluxed in 50 mL of dry toluene solvent for 18 h; cooled to room temperature, the reaction system was filtered, and after removing toluene under reduced pressure, it was purified by column chromatography with petroleum ether and ethyl acetate as the eluent in a volume ratio of 8:1 to obtain the compound 3-((2-hydroxyphenyl)-amino)naphthalene-2-one (1.66 g, yield 73.6%).

[0166] The NMR characterization data of the compound 3-((2-hydroxyphenyl)-amino)naphthalene-2-one are as follows:

[0167] 1H NMR (400MHz, C6D6): δ7.34-7.32(m,1H),7.26(dd,1H),7.21(dd,2H,J=9.1,5.2Hz),7.11(s,1H),6.93(d,1H,J=8.3Hz),6.76( td,1H,J=8.3,7.6,5.2Hz),6.70(dd,1H,J=8.6,4.2Hz),6.61(dd,1H,J=8.6,4.2Hz,),5.35(s,1H),4.20(s,2H),4.01(s,1H).

[0168] Preparation Example 5

[0169] This preparation example provides a preparation method for the compound 3-((2-hydroxy-3,5-diisopropylphenyl)-amino)naphthalene-2-one, which comprises the following steps:

[0170] The compound 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one (2.29 g, 10 mmol) shown in Preparation Example 1 was mixed with 2-hydroxy-3,5-diisopropylaniline (1.74 g, 9 mmol) in three times, 50 mg of p-toluenesulfonic acid was added as a catalyst, and the mixture was refluxed in 50 mL of dry toluene solvent for 18 hours; cooled to room temperature, the reaction system was filtered, and after removing toluene under reduced pressure, it was purified by column chromatography with petroleum ether and ethyl acetate as the eluent in a volume ratio of 10:1 to obtain the compound 3-((2-hydroxy-3,5-diisopropylphenyl)-amino)naphthalene-2-one (2.56 g, yield 84.7%).

[0171] The NMR characterization data of the compound 3-((2-hydroxy-3,5-diisopropylphenyl)-amino)naphthalene-2-one are as follows:

[0172] 1 H NMR (400MHz, C6D6): δ7.34-7.32(m,1H),7.26(dd,1H),7.21(dd,2H,J=9.1,5.2Hz),7.11(s,1H),6.43(dd,1H,J=8.3Hz ), 6.27 (dd, 1H, J = 8.5, 4.4Hz), 5.33 (s, 1H), 4.20 (s, 2H), 4.00 (s, 1H), 3.05 (hept, 1H), 2.87 (hept, 1H), 1.02 (s, 12H).

[0173] Preparation Example 6

[0174] This preparation example provides a preparation method for the compound 2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalene-2-imide))phenol, which comprises the following steps:

[0175] Under nitrogen atmosphere, the compound 3-((2-hydroxy-3,5-di-tert-butylphenyl)-amino)naphthalene-2-one (36.3 g, 100 mmol) shown in Preparation Example 2 was mixed with n-butylamine (7.46 g, 102 mmol) and added The product was purified by column chromatography using triethylamine as the eluent, using a mixture of triethylamine, petroleum ether, and ethyl acetate (3:1 volume ratio of petroleum ether to ethyl acetate, with the addition of triethylamine accounting for 2% of the total volume of petroleum ether and ethyl acetate). The product was refluxed in 500 mL of toluene for 16 h. The molecular sieves were removed by filtration, and the toluene was removed under reduced pressure to obtain the crude product. The product was purified by column chromatography using a mixture of triethylamine, petroleum ether, and ethyl acetate as the eluent, with the volume ratio of petroleum ether to ethyl acetate being 3:1, and the amount of triethylamine being 2% of the total volume of petroleum ether and ethyl acetate. The product was 2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalene-2-imide))phenol (30.8 g, 73.6% yield).

[0176] The NMR characterization data of the compound 2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalene-2-imide))phenol are as follows:

[0177] 1 H NMR (400MHz, C6D6): δ8.37 (s, 1H), 7.37 (d, 1H, J = 8.1Hz), 7.34 (d, 2H, J = 7.6Hz), 7.26 (dd, 2H, J = 7.7Hz), 6.87 (d, 1H, J = 7.6Hz), 6.46(s,1H),6.03(s,1H),3.39-3.35(m,4H),1.47(m,2H),1.41(s,9H),1.38(s,9H),1.27(m,2H),0.88(t,3H,J=7.6Hz,8.3Hz).

[0178] Preparation Example 7

[0179] This preparation example provides a preparation method for the compound 2,4-dimethyl-6-(3-(n-butylamino)naphthalene-2-imide)phenol, which comprises the following steps:

[0180] Under nitrogen atmosphere, the compound 3-((2-hydroxy-3,5-dimethylphenyl)-amino)naphthalene-2-one (27.9 g, 100 mmol) shown in Preparation Example 3 was mixed with n-butylamine (7.46 g, 102 mmol) and added The product was purified by column chromatography using triethylamine as the eluent, using a 1:1 volume ratio of petroleum ether to ethyl acetate and a triethylamine concentration of 1% of the total volume of petroleum ether and ethyl acetate. The product was refluxed in 500 mL of toluene for 16 h. The molecular sieves were removed by filtration, and the toluene was removed under reduced pressure to obtain a crude product. The product was purified by column chromatography using triethylamine as the eluent, using a 1:1 volume ratio of petroleum ether to ethyl acetate and a triethylamine concentration of 1% of the total volume of petroleum ether and ethyl acetate to obtain 2,4-dimethyl-6-(3-(n-butylamino)naphthalene-2-imino)phenol (25.5 g, 76.2% yield).

[0181] The NMR characterization data of the compound 2,4-dimethyl-6-(3-(n-butylamino)naphthalene-2-imide)phenol are as follows:

[0182] 1 H NMR (400MHz, C6D6): δ8.35 (s, 1H), 7.39 (d, 1H, J = 8.1Hz), 7.36 (d, 2H, J = 7.6Hz), 7.24 (dd, 2H, J = 7.7Hz), 6.87 (d, 1H, J = 7.6Hz), 6.4 8(s,1H),6.03(s,1H),3.39(s,2H),3.35(t,2H),2.36(s,3H),2.32(s,3H),1.47(m,2H),1.27(m,2H),0.89(t,3H,J=7.6Hz,8.3Hz).

[0183] Preparation Example 8

[0184] This preparation example provides a preparation method for the compound 2,4-di-tert-butyl-6-(3-(aniline)naphthalene-2-imide)phenol, which comprises the following steps:

[0185] Under nitrogen atmosphere, 3-((2-hydroxy-3,5-di-tert-butylphenyl)-amino)naphthalene-2-one (36.3 g, 100 mmol) and aniline (9.49 g, 102 mmol) as shown in Preparation Example 2 were mixed and added. The product was purified by column chromatography using triethylamine as the eluent, using a mixture of triethylamine, petroleum ether, and ethyl acetate (5:1 volume ratio of petroleum ether to ethyl acetate, with the addition of triethylamine accounting for 3% of the total volume of petroleum ether and ethyl acetate). The product was 2,4-di-tert-butyl-6-(3-(anilino)naphthalene-2-imino)phenol (30.4 g, 69.2% yield).

[0186] The NMR characterization data of the compound 2,4-di-tert-butyl-6-(3-(aniline)naphthalene-2-imide)phenol are as follows:

[0187] 1 H NMR (400MHz, C6D6): δ8.35(s,1H),7.38(d,1H),7.33(d,2H),7.24(dd,2H),7.03(d,2H ),6.87(d,2H),6.73-6.69(m,3H),4.74(s,1H),3.39(s,2H),1.51(s,9H),1.33(s,9H).

[0188] Preparation Example 9

[0189] This preparation example provides a method for preparing the compound 2-(3-(n-butylamino)naphthalene-2-imide)phenol, which comprises the following steps:

[0190] Under nitrogen atmosphere, 3-((2-hydroxyphenyl)-amino)naphthalene-2-one (25.1 g, 100 mmol) in Preparation Example 4 was mixed with n-butylamine (7.46 g, 102 mmol) and added. The product was purified by column chromatography using triethylamine as the eluent, using a mixture of triethylamine, petroleum ether, and ethyl acetate (the volume ratio of petroleum ether to ethyl acetate was 2:1, and the amount of triethylamine was 5% of the total volume of petroleum ether and ethyl acetate). The final product, 2-(3-(n-butylamino)naphthalene-2-imino)phenol, was obtained (24.5 g, 80.1% yield).

[0191] The NMR characterization data of the compound 2-(3-(n-butylamino)naphthalene-2-imide)phenol are as follows:

[0192] 1 H NMR (400MHz, C6D6): δ9.85 (s, 1H), 8.37 (s, 1H), 7.39 (d, 1H, J = 8.1Hz), 7.36 (d, 2H, J = 7.6Hz), 7.21 (dd, 2H, J = 7.7Hz), 6. 97(m,2H),6.81(m,1H),6.48(s,1H),3.39(s,2H),3.35(t,2H),1.47(m,2H),1.27(m,2H),0.89(t,3H,J=7.6Hz,8.3Hz).

[0193] Preparation Example 10

[0194] This preparation example provides a preparation method for the compound 2,4-diisopropyl-6-(3-(n-butylamino)naphthalene-2-imide)phenol, which comprises the following steps:

[0195] Under nitrogen atmosphere, the compound 3-((2-hydroxy-3,5-diisopropylphenyl)-amino)naphthalene-2-one (33.5 g, 100 mmol) shown in Preparation Example 5 was mixed with n-butylamine (7.46 g, 102 mmol) and added The product was purified by column chromatography using triethylamine as the eluent. The column was treated with triethylamine and the eluent consisted of triethylamine, petroleum ether, and ethyl acetate. The volume ratio of petroleum ether to ethyl acetate was 3:1, and the amount of triethylamine was 3% of the total volume of petroleum ether and ethyl acetate. The final product, 2,4-diisopropyl-6-(3-(n-butylamino)naphthalene-2-imino)phenol, was obtained (28.9 g, 73.8% yield).

[0196] The NMR characterization data of the compound 2,4-diisopropyl-6-(3-(n-butylamino)naphthalene-2-imide)phenol are as follows:

[0197] 1 H NMR (400MHz, C6D6): δ8.39(s,1H),7.34(d,2H),7.33(m,2H,),7.27(dd,2H),7.04(d,1H),4.21(s,1H),3. 39(s,2H),3.27(m,1H),3.08(m,1H),1.44(m,2H),1.38(m,2H),1.34(m,2H),1.27(t,3H),1.18(dd,12H).

[0198] The compounds 2,4-bis(trimethylphenyl)-6-(3-(isopropylamino)naphthalene-2-imine)phenol, 2,4-dichloro-6-(3-(methylamino)naphthalene-2-imine)phenol, 2,4-dimethyl-6-(3-(trimethylaniline)naphthalene-2-imine)phenol, 2,4-dimethoxy-6-(3-(chloroamine)naphthalene-2-imine)phenol and 6-(3-(n-ethylamine)naphthalene-2-imine)phenol were synthesized according to the following synthetic route. The specific equivalents of each raw material and the reaction conditions used were all referenced to the synthesis of the compound 2,4-di-tert-butyl-6-(3-(n-butylamino)naphthalene-2-imine)phenol.

[0199]

[0200] Among them, in the synthetic route of the compound 2,4-di(trimethylphenyl)-6-(3-(isopropylamine)naphthalene-2-imine)phenol, R1 is isopropyl and R2 is 2,4,6-trimethylphenyl; in the synthetic route of the compound 2,4-dichloro-6-(3-(methylamine)naphthalene-2-imine)phenol, R1 is methyl and R2 is chlorine; in the synthetic route of the compound 2,4-dimethyl-6-(3-(trimethylaniline)naphthalene-2-imine)phenol, R1 is 2,4,6-trimethylphenyl and R2 is methyl; in the synthetic route of 2,4-dimethoxy-6-(3-(chloroamine)naphthalene-2-imine)phenol, R1 is chlorine, R2 is methoxy, and formula III is ammonium chloride; in the synthetic route of the compound 6-(3-(n-ethylamine)naphthalene-2-imine)phenol, R1 is ethyl and R2 is hydrogen.

[0201] Example 1

[0202] This embodiment provides a method for preparing a metal compound L1TiMe2 (2,4-di-tert-butyl-6-(3-(n-butylamino)naphthalene-2-imine)phenol)-dimethyltitanium containing a dihydronaphthalene structure, the preparation method comprising the following steps:

[0203] Titanium tetrachloride (0.378 g, 2 mmol) was weighed and added to 40 mL of dry toluene. A 3 M methylmagnesium bromide solution (4 mL, 12 mmol) was slowly added at -40°C and stirred for 2 h. 2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalene-2-imide))phenol (0.837 g, 2 mmol) from Preparation Example 6 was added and stirred at -40°C for 2 h. After returning to room temperature, stirring was continued for 5 h. Protect from light. The solvent was removed by vortexing, and the mixture was extracted with n-hexane. Filtering afforded compound L1TiMe2 (0.80 g, 81% yield).

[0204] The NMR characterization data of the compound L1TiMe2 are as follows:

[0205] 1 H NMR (400MHz, C6D6): δ7.37(d,1H),7.34(d,2H),7.26(dd,2H),6.87(d,1H),6.46(s,1H),3.39(s,2 H,),3.11(t,2H),1.47(m,2H),1.41(s,9H),1.30(m,2H),1.27(s,9H),0.88(t,3H,),0.76(s,6H).

[0206] Example 2

[0207] The present example provides a preparation method of a metal compound L1ZrMe2 (2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalen-2-imine))phenol)-dimethylzirconium containing a dihydronaphthalene structure, which is only different from that of Example 1 in that titanium tetrachloride (0.378 g, 2 mmol) is replaced by zirconium tetrachloride (0.466 g, 2 mmol), and other raw materials, contents and preparation methods are the same as those of Example 1, to obtain compound L1ZrMe2 (0.96 g, yield 89%).

[0208] The nuclear magnetic characterization data of the compound L1ZrMe2 are as follows:

[0209] 1 H NMR (400 MHz, C6D6): δ 7.37 (d, 1H), 7.33 (d, 2H, 7.26 (dd, 2H), 6.87 (d, 1H), 6.46 (s, 1H), 3.39 (s, 2H), 3.16 (t, 2H), 1.45 (m, 4H), 1.41 (s, 9H), 1.27 (s, 9H), 0.88 (t, 3H), 0.66 (s, 6H).

[0210] Example 3

[0211] The present example provides a preparation method of a metal compound L1HfMe2 (2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalen-2-imine))phenol)-dimethylhafnium containing a dihydronaphthalene structure, which is only different from that of Example 1 in that titanium tetrachloride (0.378 g, 2 mmol) is replaced by hafnium tetrachloride (0.466 g, 2 mmol), and other raw materials, contents and preparation methods are the same as those of Example 1, to obtain compound L1HfMe2 (1.06 g, yield 85%).

[0212] The nuclear magnetic characterization data of the compound L1HfMe2 are as follows:

[0213] 1 H NMR (400 MHz, C6D6): δ 7.41 (d, 1H), 7.33 (d, 2H), 7.26 (dd, 2H), 6.87 (d, 1H), 6.46 (s, 1H), 3.39 (s, 2H,), 3.11 (t, 2H), 1.45 (m, 2H,), 1.41 (s, 9H), 1.30 (m, 2H), 1.27 (s, 9H), 0.88 (t, 3H), 0.66 (s, 6H).

[0214] Example 4

[0215] This embodiment provides a method for preparing a metal compound L2HfMe2 (2,4-dimethyl-6-(3-(n-butylamine)naphthalene-2-imine)phenol)-dimethylhafnium containing a dihydronaphthalene structure. The preparation method differs from that of Example 3 only in that the compound 2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol (0.837 g, 2 mmol) shown in Preparation Example 6 is replaced by the compound 2,4-dimethyl-6-(3-(n-butylamine)naphthalene-2-imine)phenol (0.668 g, 2 mmol) shown in Preparation Example 7. Other raw materials, contents and preparation methods are the same as those in Example 3, and compound L2HfMe2 (0.94 g, yield 87%) is obtained.

[0216] The NMR characterization data of the compound L2HfMe2 are as follows:

[0217] 1 H NMR (400MHz, C6D6): δ7.39(d,1H,J=8.1Hz,),7.36(d,2H,J=7.6Hz),7.24(dd,2H,J=7.7Hz),6.85(d,1H,J=7.6Hz),6.48(s,1 H), 3.39 (s, 2H), 3.35 (t, 2H), 2.36 (s, 3H), 2.15 (s, 3H), 1.47 (m, 2H), 1.27 (m, 2H), 0.89 (t, 3H, J = 7.6Hz, 8.3Hz), 0.77 (s, 6H).

[0218] Example 5

[0219] This embodiment provides a method for preparing a metal compound L3HfMe2 (2,4-di-tert-butyl-6-(3-(aniline)naphthalene-2-imine)phenol)-dimethylhafnium containing a dihydronaphthalene structure. The preparation method differs from that of Example 3 only in that the compound 2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol (0.837 g, 2 mmol) shown in Preparation Example 6 is replaced by the compound 2,4-di-tert-butyl-6-(3-(aniline)naphthalene-2-imine)phenol (0.877 g, 2 mmol) shown in Preparation Example 8. The other raw materials, contents and preparation methods are the same as those in Example 3, and the compound L3HfMe2 (1.08 g, yield 83.6%) is obtained.

[0220] The NMR characterization data of the compound L3HfMe2 are as follows:

[0221] 1H NMR (400MHz, C6D6): δ7.38(d,2H),7.33(d,3H),7.24(dd,2H),7.18(d,2H ),6.73-6.69(m,3H),3.39(s,2H),1.41(s,9H),1.27(s,9H),0.78(s,6H).

[0222] Example 6

[0223] This embodiment provides a method for preparing a metal compound L5HfMe2 (2,4-diisopropyl-6-(3-(n-butylamine)naphthalene-2-imine)phenol)-dimethylhafnium containing a dihydronaphthalene structure. The preparation method differs from that of Example 3 only in that the compound 2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol (0.837 g, 2 mmol) shown in Preparation Example 6 is replaced by the compound 2,4-diisopropyl-6-(3-(n-butylamine)naphthalene-2-imine)phenol (0.78 g, 2 mmol) shown in Preparation Example 10. The other raw materials, contents and preparation methods are the same as those in Example 3, and the compound L5HfMe2 (0.907 g, yield 76%) is obtained.

[0224] The NMR characterization data of the compound L5HfMe2 are as follows:

[0225] 1 H NMR (400MHz, C6D6): δ7.39(d,1H),7.36(d,2H),7.24(dd,2H),6.85(d,1H),6.48(s,1H),3.39(s,2 H),3.35(t,2H),2.15(s,2H),1.47(m,2H),1.33(dd,12H),1.27(m,2H,),0.89(t,3H),0.77(s,6H).

[0226] Example 7

[0227] This embodiment provides a method for preparing a metal compound L6TiMe2 (2,4-di(trimethylphenyl)-6-(3-(isopropylamino)naphthalene-2-imine)phenol)-dimethyltitanium containing a dihydronaphthalene structure. The preparation method differs from that in Example 1 only in that the compound 2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalene-2-imine))phenol (0.837 g, 2 mmol) shown in Preparation Example 6 is replaced by the compound 2,4-di(trimethylphenyl)-6-(3-(isopropylamino)naphthalene-2-imine)phenol (1.2 g, 2 mmol). The other raw materials, contents and preparation methods are the same as those in Example 1, and the compound L6TiMe2 (1 g, yield 83.5%) is obtained.

[0228] The NMR characterization data of the compound L6TiMe2 are as follows:

[0229] 1 H NMR (400MHz, C6D6): δ7.39(d,1H),7.36(d,2H),7.24(m,6H),6.85(d,1H),6.48(s,1H),3. 47(m,1H),3.41(t,2H),3.39(s,6H),3.35(t,6H),3.15(s,6H),1.27(d,6H,),0.77(s,6H).

[0230] Example 8

[0231] This example provides a method for preparing a metal compound L7TiBn2 (2,4-dichloro-6-(3-(methylamine)naphthalene-2-imine)phenol)-dibenzyltitanium containing a dihydronaphthalene structure. The difference between the preparation method and Example 1 is that the 3M methylmagnesium bromide solution (4mL, 12mmol) is replaced by a 1M benzylmagnesium bromide solution (12mL, 12mmol), and the compound 2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol (0.837g, 2mmol) shown in Preparation Example 6 is replaced by the compound 2,4-dichloro-6-(3-(methylamine)naphthalene-2-imine)phenol (0.66g, 2mmol). The other raw materials, contents and preparation methods are the same as those in Example 1, and the compound L7TiBn2 (0.91g, yield 81.2%) is obtained.

[0232] The NMR characterization data of the compound L7TiBn2 are as follows:

[0233] 1 H NMR (400MHz, C6D6): δ7.39(m,3H),7.36(d,3H),7.24(m,3H),6.85(d,4H),6.48(s,4H),3.41(t,2H),3.39(s,3H),2.83(s,4H).

[0234] Example 9

[0235] This embodiment provides a method for preparing a metal compound L8ZrCl2 (2,4-dimethyl-6-(3-(trimethylanilino)naphthalene-2-imine)phenol)-zirconium dichloride containing a dihydronaphthalene structure, the preparation method comprising the following steps:

[0236] Zirconium tetrachloride (0.466 g, 2 mmol) was weighed and added to 40 mL of dry toluene. 2,4-dimethyl-6-(3-(trimethylanilino)naphthalene-2-imino)phenol (0.792 g, 2 mmol) was then added at -40°C. Stir for 2 hours, then return to room temperature and continue stirring for 5 hours. Protect from light. The solvent was removed by vortexing, and the mixture was extracted with n-hexane and filtered to obtain compound L8ZrCl2 (0.94 g, 84.4% yield).

[0237] The NMR characterization data of the compound L8ZrCl2 are as follows:

[0238] 1 H NMR (400MHz, C6D6): δ7.39(d,1H),7.36(d,2H),7.24(dd,2H),6.85(d,2H),6.48(s,2H),3.39(s,2H),2.35(s,3H),2.15(s,12H).

[0239] Example 10

[0240] This example provides a method for preparing a metal compound L9ZrMe2 (2,4-dimethoxy-6-(3-(chloroamine)naphthalene-2-imine)phenol)-dimethylzirconium containing a dihydronaphthalene structure. The difference between the preparation method and Example 2 is that the compound 2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol (0.837 g, 2 mmol) shown in Preparation Example 6 is replaced by the compound 2,4-dimethoxy-6-(3-(chloroamine)naphthalene-2-imine)phenol (0.688 g, 2 mmol). The other raw materials, contents and preparation methods are the same as those in Example 2, and the compound L9ZrMe2 (0.8 g, yield 86.6%) is obtained.

[0241] The NMR characterization data of the compound L9ZrMe2 are as follows:

[0242] 1 H NMR (400MHz, C6D6): δ7.39(d,1H),7.36(d,2H),7.24(dd,2H),6.85(d,1H),6.48(s,1H),3.89(s,6H),3.35(t,2H),0.77(s,6H).

[0243] Example 11

[0244] This embodiment provides a method for preparing a metal compound L10Ti(N(CH3)2)2(6-(3-(n-ethylamino)naphthalene-2-imine)phenol)-bis(dimethylamino)titanium containing a dihydronaphthalene structure, the preparation method comprising the following steps:

[0245] Tetrakis(N,N-dimethylamino)titanium (0.44 g, 2 mmol) was weighed and added to 40 mL of dry toluene. 6-(3-(n-ethylamino)naphthalene-2-imino)phenol (0.456 g, 2 mmol) was then added at 80°C and stirred for 6 h. Protect from light. The solvent was removed by vortexing, and the mixture was extracted with n-hexane and filtered to obtain compound L10Ti(N(CH3)2)2 (0.64 g, 77.2% yield). The NMR characterization data of compound L10Ti(N(CH3)2)2 are as follows:

[0246] 1 H NMR (400MHz, C6D6): δ7.39(m,1H),7.36(d,2H),7.24(m,2H),6.85(d,2H),6.48(s,2H),4.41(t,2H),3.39(m,2H),2.63(s,12H),1.32(t,3H).

[0247] Application Example 1

[0248] This application example provides an application of a catalyst composition containing L1TiMe2 in catalyzing the copolymerization of ethylene and 1-octene. The catalyst composition includes L1TiMe2, activators silica gel and MAO, and a co-catalyst triisobutylaluminum.

[0249] Preparation of the primary catalyst: Grace 955 silica gel was calcined in a muffle furnace at 200°C for 2 hours, followed by calcination at 600°C for 4 hours. Six grams of the calcined silica gel was added to 100 mL of a 10 wt% MAO toluene solution. The mixture was stirred at 55°C for 4 hours and filtered to dryness, yielding MAO-silica gel. Subsequently, 2 grams of L1TiMe2 was dissolved in 20 mL of toluene, to which 6 grams of MAO-silica gel was added. The mixture was stirred at 55°C for 6 hours and filtered to dryness, yielding the primary catalyst.

[0250] A 2L polymerization reactor was dried continuously at 120°C for 6 hours. While still hot, the reactor was evacuated and replaced with N2 three times. The reactor was cooled to room temperature and replaced with ethylene three times. 533mL of n-hexane, 347mL / 250g of 1-octene, and 1.5mL of a 0.5M solution of triisobutylaluminum in diethyl ether were added. The temperature was adjusted to 25°C, and 3mg of the above-mentioned primary catalyst was added. The ethylene pressure was adjusted to 4MPa and maintained constant. The reactor was stirred vigorously for 30 minutes. After the reaction was complete, the reactor was cooled to room temperature and the pressure was released. The reaction mixture was neutralized with 5% hydrochloric acid in ethanol to obtain a polymer precipitate. The precipitate was washed with ethanol and water, and then vacuum-dried to a constant weight. 73.2g of copolymer was weighed.

[0251] Application Example 2

[0252] This application example provides an application of a catalyst composition containing L1ZrMe2 in catalyzing the copolymerization of ethylene and 1-octene. The only difference from Application Example 1 is that L1TiMe2 is replaced by L1ZrMe2. The other reaction conditions and polymerization reaction process are the same as those in Application Example 1, and 127.4 g of polymer is obtained.

[0253] Application Example 3

[0254] This application example provides an application of a catalyst composition containing L1HfMe2 in catalyzing the copolymerization of ethylene and 1-octene. The only difference from Application Example 1 is that L1TiMe2 is replaced by L1HfMe2. The other reaction conditions and polymerization reaction process are the same as those in Application Example 1, and 141.3 g of polymer is obtained.

[0255] Application Example 4

[0256] This application example provides an application of a catalyst composition containing L2HfMe2 in catalyzing the copolymerization of ethylene and 1-octene. The only difference from Application Example 1 is that L1TiMe2 is replaced by L2HfMe2. The other reaction conditions and polymerization reaction process are the same as those in Application Example 1, and 219.2 g of polymer is obtained.

[0257] Application Example 5

[0258] This application example provides an application of a catalyst composition containing L3HfMe2 in catalyzing the copolymerization of ethylene and 1-octene. The only difference from Application Example 1 is that L1TiMe2 is replaced by L3HfMe2. The other reaction conditions and polymerization reaction process are the same as those in Application Example 1, and 104.7 g of polymer is obtained.

[0259] Application Example 6

[0260] This application example provides an application of a catalyst composition containing L5HfMe2 in catalyzing ethylene homopolymerization. The catalyst composition includes L5HfMe2, activators silica gel and MAO, and a co-catalyst triisobutylaluminum.

[0261] Preparation of the primary catalyst: Grace 955 silica gel was calcined in a muffle furnace at 200°C for 2 hours, followed by calcination at 600°C for 4 hours. Six grams of the calcined silica gel was added to 100 mL of a 10 wt% MAO toluene solution. The mixture was stirred at 55°C for 4 hours and filtered to dryness, yielding MAO-silica gel. Subsequently, 2 grams of L5HfMe2 was dissolved in 20 mL of toluene, to which 6 grams of MAO-silica gel was added. The mixture was stirred at 55°C for 6 hours and filtered to dryness, yielding the primary catalyst.

[0262] A 2L polymerization reactor was continuously dried at 120℃ for 6h, vacuumized while hot and replaced with N2for 3 times, cooled to room temperature, replaced with ethylene for 3 times. 500mL of n-hexane was added, 1.5mL of 0.5M triisobutylaluminum ethyl ether solution was added; the temperature was 25℃, 3mg of the main catalyst was added, the ethylene pressure was adjusted to 4MPa and kept unchanged; the reaction was stirred vigorously for 30min. After the reaction was completed, the temperature was cooled to room temperature, the pressure was removed; the reaction solution was neutralized with 5% hydrochloric acid acidified ethanol solution to obtain a polymer precipitate, which was washed with ethanol and water, and vacuum dried to constant weight to obtain 66.7g of copolymer.

[0263] Application Example 7

[0264] This application example provides an application of a catalyst composition containing L6TiMe2 in catalyzing ethylene homopolymerization, which is different from application example 6 only in that L5HfMe2 is replaced by L6TiMe2, and other reaction conditions and polymerization processes are the same as those in application example 6, and 133.5g of polymer is obtained.

[0265] Application Example 8

[0266] This application example provides an application of a catalyst composition containing L7TiBn2 in catalyzing ethylene homopolymerization, which is different from application example 6 only in that L5HfMe2 is replaced by L7TiBn2, and other reaction conditions and polymerization processes are the same as those in application example 6, and 143.2g of polymer is obtained.

[0267] Application Example 9

[0268] This application example provides an application of a catalyst composition containing L8ZrCl2 in catalyzing 4-methyl-1-pentene and 1-hexene copolymerization, which includes L8ZrCl2, activator silica gel and MAO, and cocatalyst triisobutylaluminum.

[0269] Preparation of the main catalyst: 955 type silica gel produced by Grace was selected, calcined at 200℃ for 2h in a muffle furnace, and then calcined at 600℃ for 4h. 6g of the calcined silica gel was weighed, 100mL of 10wt% MAO toluene solution was added, stirred at 55℃ for 4h, filtered and dried to obtain MAO-silica gel. Then 2g of L8ZrCl2 was weighed, dissolved in 20mL of toluene, 6g of MAO-silica gel was added, stirred at 55℃ for 6h, filtered and dried to obtain the main catalyst.

[0270] A 2L polymerization reactor was dried continuously at 120°C for 6 hours. While still hot, the reactor was evacuated and replaced with N2 three times, then cooled to room temperature. 500mL of n-hexane, 300mL / 198g of 4-methyl-1-pentene, 6mL of 1-hexene, and 1.5mL of a 0.5M solution of triisobutylaluminum in diethyl ether were added. The temperature was maintained at 25°C, and 3mg of the primary catalyst was added. The reaction was stirred vigorously for 30 minutes. After the reaction was complete, the reactor was cooled to room temperature and the pressure was released. The reaction solution was neutralized with 5% hydrochloric acid in ethanol to obtain a polymer precipitate. The precipitate was washed with ethanol and water, and then vacuum-dried to a constant weight. 73.1g of the copolymer was weighed.

[0271] Application Example 10

[0272] This application example provides an application of a catalyst composition containing L9ZrMe2 in catalyzing the copolymerization of 4-methyl-1-pentene and 1-hexene. The only difference from Application Example 9 is that L8ZrCl2 is replaced by L9ZrMe2. The other reaction conditions and polymerization reaction process are the same as those in Application Example 9, and 113.6 g of polymer is obtained.

[0273] Application Example 11

[0274] This application example provides an application of a catalyst composition containing L10Ti(N(CH3)2)2 in catalyzing the copolymerization of 4-methyl-1-pentene and 1-hexene. The only difference from Application Example 9 is that L8ZrCl2 is replaced by L10Ti(N(CH3)2)2. The other reaction conditions and polymerization reaction process are the same as those in Application Example 9, and 128.2 g of polymer is obtained.

[0275] Comparative Application Example 1

[0276] This application example provides an application of a catalyst composition in catalyzing the copolymerization of ethylene and 1-octene. The only difference from Application Example 1 is that L1TiMe2 is replaced by M1 (its synthesis reference patent CN1461756A, Example 2). The other reaction conditions and polymerization reaction process are the same as those in Application Example 1, and 1.4 g of polymer is obtained.

[0277]

[0278] Comparative Application Example 2

[0279] This application example provides an application of a catalyst composition in catalyzing the copolymerization of ethylene and 1-octene. The only difference from Application Example 1 is that L1TiMe2 is replaced by M2 (its synthesis reference patent CN1472230A, Synthesis Example 13). The other reaction conditions and polymerization reaction process are the same as those in Application Example 1, and 0.42 g of polymer is obtained.

[0280]

[0281] Comparative Application Example 3

[0282] This application example provides an application of a catalyst composition in catalyzing the copolymerization of ethylene and 1-octene. The only difference from Application Example 1 is that the catalyst composition does not contain L1TiMe2. The other reaction conditions and polymerization reaction process are the same as those in Application Example 1. No polymer is obtained and the reaction system is inactive.

[0283] The aggregation results of use cases 1-11 and comparative application cases 1-2 were tested using the following method:

[0284] Polymerization activity test: calculated according to the formula "polymerization activity = polymer mass / (catalyst mass)";

[0285] Polymer weight-average molecular weight and molecular weight distribution: measured by PL-GPC220 at 150°C using three PLgel 10μm MIXED-B columns in series and 1,2,4-trichlorobenzene as the solvent.

[0286] Melting point test: measured according to the conventional DSC (2000) method;

[0287] Comonomer insertion rate: According to the reference (Liu W, Ray DG, Rinaldi P L. Resolution of Signals from Long-Chain Branching in Polyethylene by 13 C NMR at 188.6MHz[J].Macromolecules,1999,32(11).) was tested at high temperature and calculated; high temperature 13C NMR was obtained at 120℃ using Brucker DMX 300MHz with 1,1,2,2-tetrachloroethane as solvent;

[0288] Extraction rate test: Weigh 5g of polymer and place it on the top of the Soxhlet extractor. Add n-hexane to the flask and reflux at 70℃.

[0289] Extraction rate = mass of extracted substance / total mass of substance*100%;

[0290] Bulk density test: Use the weighing method to test. Weigh 10g (accurate to 0.1%) of the sample and place it in a 100mL graduated cylinder. Level the sample powder without compacting it, and read the apparent volume V.

[0291]

[0292] The test results of Application Examples 1-5 and Comparative Application Examples 1-2 are shown in Table 1:

[0293] Table 1

[0294]

[0295] The test results of application examples 6-8 are shown in Table 2:

[0296] Table 2

[0297]

[0298] The test results of application examples 9-11 are shown in Table 3:

[0299] Table 3

[0300]

[0301]

[0302] The test results show that:

[0303] As can be seen from Tables 1-3 above, the catalyst composition prepared from the metal compound containing a dihydronaphthalene structure provided by the present invention exhibits high activity in the copolymerization of ethylene with α-olefins such as 1-hexene and 1-octene, and produces copolymers with high molecular weight, high comonomer insertion rate, and narrow molecular weight distribution. The polymers have a high bulk density.

[0304] As shown in Table 1, when catalyzing the copolymerization of ethylene and 1-octene at 25°C, the activity can reach 73.1 kg / g (catalyst) and the weight average molecular weight can reach 1364×10 3 g / mol, a molecular weight distribution of no more than 2.3, an insertion rate of 1-octene can reach 61.8wt%, a bulk density of 0.71g / mL, and an extraction rate of only 0.02-0.07wt%; by comparing Application Example 1 with Comparative Application Example 1 and Comparative Application Example 2, it can be seen that the catalyst composition prepared by using a metal compound containing a dihydronaphthalene structure that is not specific to the present invention has poor catalytic activity in catalyzing olefin copolymerization reactions, the molecular weight of the prepared polymer is not high, and its molecular weight distribution is much higher than 2.3. At the same time, the polymer has a low bulk density and an extraction rate much higher than 0.07%, which cannot meet the actual production requirements for high catalyst activity, high insertion rate and narrow molecular weight distribution, and is also not conducive to the preparation of a polymer with high bulk density and low extraction.

[0305] As shown in Table 2, when catalyzing ethylene homopolymerization at 25°C, the activity is as high as 95.5 kg / g (catalyst), and the weight average molecular weight can reach 1027×10 3g / mol, the molecular weight distribution is no higher than 3, the bulk density can reach 0.89 g / mL, and the extraction rate is only 0.03-0.05wt%.

[0306] As shown in Table 3, when catalyzing the copolymerization of 4-methyl-1-pentene and 1-hexene at 25°C, the activity can reach 85.7 kg / g (catalyst), and the weight average molecular weight can reach 1247×10 3 g / mol, the molecular weight distribution is no higher than 2.5, the melting point of poly 4-methyl-1pentene can reach 236 ° C, the bulk density can reach 0.83 g / mL, and the extraction rate is only 0.02-0.06 wt%.

[0307] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A metal compound containing a dihydronaphthalene structure, characterized in that: The metal compound containing a dihydronaphthalene structure has a structure shown in formula (I): wherein R1 is selected from hydrogen, halogen, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 18 Aryl, substituted or unsubstituted C4-C 18 Heteroaryl; R2 is selected from hydrogen, halogen, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Cycloalkyl, substituted or unsubstituted C1-C 16 alkoxy; X is selected from halogen, substituted or unsubstituted C1-C 20 Alkyl, -NR4R5; said R4 and R5 are the same or different, each independently selected from C 1-8 alkyl; M is selected from Group IVB metals; When the group contains heteroatoms, the heteroatoms are selected from one or a combination of at least two of O, S, N, P, and Si; The substituted groups are selected from halogen, C1-C8 alkyl, C1-C8 alkoxy, C6-C 10 Aryl, C6-C 10 Heteroaryl.

2. The metal compound containing a dihydronaphthalene structure according to claim 1, characterized in that R1 is selected from hydrogen, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 14 Aryl, substituted or unsubstituted C4-C 12 Heteroaryl.

3. The metal compound containing a dihydronaphthalene structure according to claim 2, characterized in that R1 is selected from hydrogen, chlorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-tert-butylphenyl, 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl.

4. The metal compound containing a dihydronaphthalene structure according to claim 1, characterized in that R2 is selected from hydrogen, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C8 alkoxy.

5. The metal compound containing a dihydronaphthalene structure according to claim 4, characterized in that R2 is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or methoxy.

6. The metal compound containing a dihydronaphthalene structure according to claim 1, characterized in that X is selected from halogen, substituted or unsubstituted C1-C4 alkyl, -NR4R5, wherein R4 and R5 are the same or different and are independently selected from C 1-8 alkyl.

7. The metal compound containing a dihydronaphthalene structure according to claim 6, characterized in that X is selected from chlorine, methyl, benzyl or dimethylamino.

8. The metal compound containing a dihydronaphthalene structure according to claim 1, characterized in that M is selected from titanium, zirconium or hafnium.

9. The metal compound containing a dihydronaphthalene structure according to claim 1, characterized in that The metal compound containing a dihydronaphthalene structure is selected from any one of the following compounds:

10. A method for preparing a metal compound containing a dihydronaphthalene structure according to any one of claims 1 to 9, characterized in that: The preparation method comprises the following steps: (1) 1,4-dihydro-naphthalene-2,3-dione reacts with morpholine to obtain the intermediate 2-(4-morpholino)-1,4-dihydro-naphthalene-3-one; (2) mixing the intermediate 2-(4-morpholino)-1,4-dihydro-naphthalen-3-one described in step (1) with the compound represented by formula II, adding a catalyst, and reacting to obtain intermediate 2; (3) mixing the intermediate 2 described in step (2) with the compound represented by formula III, adding a desiccant and a catalyst, and reacting to obtain intermediate 3; (4) mixing the compound represented by Formula IV and the compound represented by Formula V, and adding the intermediate 3 described in step (3) to carry out reaction a to obtain the metal compound containing a dihydronaphthalene structure; Alternatively, the compound represented by formula IV is directly added to the intermediate 3 described in step (3) to carry out reaction b to obtain the metal compound containing a dihydronaphthalene structure; Alternatively, the compound represented by formula VI is directly added to the intermediate 3 described in step (3) to carry out reaction c to obtain the metal compound containing a dihydronaphthalene structure; 11. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The reactions in steps (1) to (4) are carried out in an anhydrous solvent, which includes any one of benzene, toluene, xylene or n-hexane, or a combination of at least two thereof.

12. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The molar ratio of 1,4-dihydro-naphthalene-2,3-dione to morpholine in step (1) is 1:(0.9-1).

13. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The reaction in step (1) is carried out under reflux.

14. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The reaction time of step (1) is 5 to 10 hours.

15. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: After the reaction in step (1) is completed, the anhydrous solvent is removed by vortexing under reduced pressure.

16. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The molar ratio of the 2-(4-morpholine)-1,4-dihydro-naphthalen-3-one in step (2) to the compound represented by formula II is 1:(0.6-1.0).

17. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The compound represented by formula II in step (2) is added in batches.

18. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 17, wherein: The compound represented by formula II in step (2) is added in three batches.

19. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The mixing in step (2) is carried out under stirring.

20. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The molar ratio of the 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one in step (2) to the catalyst is 1:(0.0058-0.029).

21. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The catalyst in step (2) comprises p-toluenesulfonic acid.

22. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The reaction in step (2) is carried out under reflux.

23. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The reaction time of step (2) is 10 to 18 hours.

24. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: After the reaction in step (2) is completed, the reaction solution is cooled to room temperature, filtered, and the anhydrous solvent is removed by vortexing under reduced pressure. Intermediate 2 is obtained by column chromatography.

25. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 24, wherein: The eluents in the column chromatography are petroleum ether and ethyl acetate, and the volume ratio thereof is (1-20):

1.

26. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The molar ratio of the intermediate 2 in step (3) to the compound represented by formula III is 1:(1-5).

27. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The mixing in step (3) is carried out under stirring.

28. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The desiccant in step (3) includes molecular sieve.

29. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The catalyst in step (3) includes formic acid.

30. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The molar ratio of the intermediate 2 to the catalyst in step (3) is 1:(0.1-0.5).

31. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The reaction in step (3) is carried out under reflux.

32. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The reaction time of step (3) is 10 to 18 hours.

33. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: After the reaction in step (3) is completed, the reaction solution is filtered to remove the desiccant, the anhydrous solvent is removed under reduced pressure, and column chromatography is performed to obtain intermediate 3.

34. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 33, wherein: The column used for the column chromatography was treated with triethylamine.

35. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 33, wherein: The eluent used for the column chromatography includes petroleum ether and ethyl acetate, and the volume ratio thereof is (1:50) to (100:1).

36. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 35, wherein: The eluent also includes triethylamine.

37. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 36, wherein: The added volume of the triethylamine is 1-5% of the total added volume of the petroleum ether and ethyl acetate.

38. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: In step (4), the compound represented by formula IV is dissolved in an anhydrous solvent before being mixed and stirred with the compound represented by formula V.

39. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: When the amount of the compound represented by formula IV added in step (4) is 1 mmol, the volume of the anhydrous solvent added is 15 to 50 mL.

40. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The molar ratio of formula IV, formula V and intermediate 3 in the reaction a of step (4) is 1:(4-6):

1.

41. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The mixing and stirring in step (4) is carried out at low temperature.

42. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 41, wherein: The low temperature is -45°C to 10°C.

43. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The stirring time in step (4) is 1.5 to 2.5 hours.

44. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: In step (4), the reaction a is first stirred at -45°C to 10°C for 1.5 to 2.5 hours, and then heated to room temperature and stirred for 4 to 6 hours.

45. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The molar ratio of formula IV to intermediate 3 in the reaction b of step (4) is 1:(1-2).

46. ​​The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: In step (4), the reaction b is first stirred at -45°C to 10°C for 1.5 to 2.5 hours, and then heated to room temperature and stirred for 4 to 6 hours.

47. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The molar ratio of Formula VI to Intermediate 3 in the reaction c of step (4) is 1:(1-2).

48. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The reaction c in step (4) is stirred at 50°C to 100°C for 4 to 10 hours.

49. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: After the reaction a, b or c in step (4) is completed, the anhydrous solvent is removed under reduced pressure, and extraction is performed with a good solvent to obtain the metal compound containing a dihydronaphthalene structure.

50. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 10, wherein: The reactions in steps (1), (3) and (4) are all carried out under a protective gas atmosphere, wherein the protective gas comprises any one of nitrogen, argon and helium or a combination of at least two of them.

51. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 49, wherein: The good solvent in step (4) includes any one of n-hexane, n-pentane, n-heptane, cyclohexane, methylcyclohexane or toluene, or a combination of at least two thereof.

52. A catalyst composition for polymerizing olefins, characterized in that The catalyst composition comprises the metal compound containing a dihydronaphthalene structure according to any one of claims 1 to 9, a co-catalyst and an activator.

53. The catalyst composition according to claim 52, characterized in that The molar ratio of the co-catalyst to the metal compound containing a dihydronaphthalene structure according to any one of claims 1 to 9 is (0.001 to 100,000):

1.

54. The catalyst composition according to claim 53, characterized in that The molar ratio of the co-catalyst to the metal compound containing a dihydronaphthalene structure is (0.2-500):

1.

55. The catalyst composition according to claim 52, characterized in that The co-catalyst includes an organometallic compound and / or an organoboron compound.

56. The catalyst composition according to claim 55, characterized in that The organometallic compound and / or organoboron compound includes M 3 (X 10 ) n1 (X 11 ) 3-n1 、M 4 (X 10 ) n2 (X 11 ) 2-n2 or M 5 X 10 Any of the following; Among them, M 3 is boron or aluminum, n1 is 1-3; M 4 is magnesium or zinc, n2 is 1-2; M 5 For Li; X 10 Selected from hydrogen, C1-C 20 Hydrocarbon; X 11 Selected from hydrogen, halogen, C1-C 20 Hydrocarbon or C1-C 20 Hydrocarbyloxy.

57. The catalyst composition according to claim 56, characterized in that The M 3 (X 10 ) n1 (X 11 ) 3-n1 The present invention includes any one or a combination of at least two of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide or diethylaluminum chloride.

58. The catalyst composition according to claim 56, characterized in that The M 4 (X 10 ) n2 (X 11 ) 2-n2 The present invention comprises any one of dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc or dineopentylzinc, or a combination of at least two thereof.

59. The catalyst composition according to claim 52, characterized in that The activator includes any one of an organic boron compound, an organic borate compound, an ionizing ionic compound, an aluminoxane compound or a solid oxide, or a combination of at least two thereof.

60. The catalyst composition according to claim 59, characterized in that The solid oxide includes any one of silica, alumina, titania, zirconia, magnesia, boria, calcium oxide, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, silica-boria, alumina-titania, titania-zirconia, alumina-zirconia, alumina-boria, zinc aluminate, aluminum phosphate, aluminum phosphate, aluminum phosphate-silica, magnesium aluminate, boehmite or heteropolytungstate, or a combination of at least two thereof.

61. The catalyst composition according to claim 59, characterized in that The solid oxide has a particle size of 20-100 μm and a specific surface area of ​​170-570 m 2 / g, pore volume 0.36-2.6mL / g, pore diameter 6-54nm, density 0.3g / cm 3 .

62. The catalyst composition according to claim 59, characterized in that The solid oxide needs to be calcined.

63. The catalyst composition according to claim 62, characterized in that The calcination includes low-temperature calcination and high-temperature calcination.

64. The catalyst composition according to claim 63, characterized in that The temperature of the low-temperature calcination is 200-500°C.

65. The catalyst composition according to claim 64, characterized in that The temperature of the low-temperature calcination is 200-300°C.

66. The catalyst composition according to claim 63, characterized in that The low-temperature calcination time is 1 to 10 hours.

67. The catalyst composition according to claim 66, characterized in that The low-temperature roasting time is 2 to 5 hours.

68. The catalyst composition according to claim 63, characterized in that The high temperature calcination temperature is 600-900°C.

69. The catalyst composition according to claim 63, characterized in that The high-temperature calcination time is 4 to 40 hours.

70. The catalyst composition according to claim 69, characterized in that The high-temperature calcination time is 4 to 10 hours.

71. Use of the metal compound containing a dihydronaphthalene structure according to any one of claims 1 to 9 or the catalyst composition according to any one of claims 52 to 70 in olefin polymerization.

72. The use according to claim 71, characterized in that The olefin monomers in the olefin polymerization reaction include any one of ethylene, propylene, butene, pentene, hexene, heptene, octene, styrene or 4-methyl-1-pentene, or a combination of at least two thereof.

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